30.5 Applications of Atomic Excitations and De-Excitations

Summary

Define and discuss fluorescence.

Define metastable.

Describe how laser emission is produced.

Explain population inversion.

Define and discuss holography.

Many properties of matter and phenomena in nature are directly related to atomic energy levels and their associated excitations and de-excitations. The color of a rose, the output of a laser, and the transparency of air are but a few examples. (See Figure 1.) While it may not appear that glow-in-the-dark pajamas and lasers have much in common, they are in fact different applications of similar atomic de-excitations.

Figure 1. Light from a laser is based on a particular type of atomic de-excitation. (credit: Jeff Keyzer)

The color of a material is due to the ability of its atoms to absorb certain wavelengths while reflecting or reemitting others. A simple red material, for example a tomato, absorbs all visible wavelengths except red. This is because the atoms of its hydrocarbon pigment (lycopene) have levels separated by a variety of energies corresponding to all visible photon energies except red. Air is another interesting example. It is transparent to visible light, because there are few energy levels that visible photons can excite in air molecules and atoms. Visible light, thus, cannot be absorbed. Furthermore, visible light is only weakly scattered by air, because visible wavelengths are so much greater than the sizes of the air molecules and atoms. Light must pass through kilometers of air to scatter enough to cause red sunsets and blue skies.

Fluorescence and Phosphorescence

The ability of a material to emit various wavelengths of light is similarly related to its atomic energy levels. Figure 2 shows a scorpion illuminated by a UV lamp, sometimes called a black light. Some rocks also glow in black light, the particular colors being a function of the rock’s mineral composition. Black lights are also used to make certain posters glow.

Figure 2. Objects glow in the visible spectrum when illuminated by an ultraviolet (black) light. Emissions are characteristic of the mineral involved, since they are related to its energy levels. In the case of scorpions, proteins near the surface of their skin give off the characteristic blue glow. This is a colorful example of fluorescence in which excitation is induced by UV radiation while de-excitation occurs in the form of visible light. (credit: Ken Bosma, Flickr)

In the fluorescence process, an atom is excited to a level several steps above its ground state by the absorption of a relatively high-energy UV photon. This is called atomic excitation. Once it is excited, the atom can de-excite in several ways, one of which is to re-emit a photon of the same energy as excited it, a single step back to the ground state. This is called atomic de-excitation. All other paths of de-excitation involve smaller steps, in which lower-energy (longer wavelength) photons are emitted. Some of these may be in the visible range, such as for the scorpion in Figure 2. Fluorescence is defined to be any process in which an atom or molecule, excited by a photon of a given energy, and de-excites by emission of a lower-energy photon.

Fluorescence can be induced by many types of energy input. Fluorescent paint, dyes, and even soap residues in clothes make colors seem brighter in sunlight by converting some UV into visible light. X rays can induce fluorescence, as is done in x-ray fluoroscopy to make brighter visible images. Electric discharges can induce fluorescence, as in so-called neon lights and in gas-discharge tubes that produce atomic and molecular spectra. Common fluorescent lights use an electric discharge in mercury vapor to cause atomic emissions from mercury atoms. The inside of a fluorescent light is coated with a fluorescent material that emits visible light over a broad spectrum of wavelengths. By choosing an appropriate coating, fluorescent lights can be made more like sunlight or like the reddish glow of candlelight, depending on needs. Fluorescent lights are more efficient in converting electrical energy into visible light than incandescent filaments (about four times as efficient), the blackbody radiation of which is primarily in the infrared due to temperature limitations.

This atom is excited to one of its higher levels by absorbing a UV photon. It can de-excite in a single step, re-emitting a photon of the same energy, or in several steps. The process is called fluorescence if the atom de-excites in smaller steps, emitting energy different from that which excited it. Fluorescence can be induced by a variety of energy inputs, such as UV, x-rays, and electrical discharge.

The spectacular Waitomo caves on North Island in New Zealand provide a natural habitat for glow-worms. The glow-worms hang up to 70 silk threads of about 30 or 40 cm each to trap prey that fly towards them in the dark. The fluorescence process is very efficient, with nearly 100% of the energy input turning into light. (In comparison, fluorescent lights are about 20% efficient.)

Fluorescence has many uses in biology and medicine. It is commonly used to label and follow a molecule within a cell. Such tagging allows one to study the structure of DNA and proteins. Fluorescent dyes and antibodies are usually used to tag the molecules, which are then illuminated with UV light and their emission of visible light is observed. Since the fluorescence of each element is characteristic, identification of elements within a sample can be done this way.

Figure 3 shows a commonly used fluorescent dye called fluorescein. Below that, Figure 4 reveals the diffusion of a fluorescent dye in water by observing it under UV light.

Nano-Crystals

Recently, a new class of fluorescent materials has appeared—“nano-crystals.” These are single-crystal molecules less than 100 nm in size. The smallest of these are called “quantum dots.” These semiconductor indicators are very small (2–6 nm) and provide improved brightness. They also have the advantage that all colors can be excited with the same incident wavelength. They are brighter and more stable than organic dyes and have a longer lifetime than conventional phosphors. They have become an excellent tool for long-term studies of cells, including migration and morphology. (Figure 5.)

Once excited, an atom or molecule will usually spontaneously de-excite quickly. (The electrons raised to higher levels are attracted to lower ones by the positive charge of the nucleus.) Spontaneous de-excitation has a very short mean lifetime of typically about [latex]{10^{-8} \;\textbf{s}}[/latex]. However, some levels have significantly longer lifetimes, ranging up to milliseconds to minutes or even hours. These energy levels are inhibited and are slow in de-exciting because their quantum numbers differ greatly from those of available lower levels. Although these level lifetimes are short in human terms, they are many orders of magnitude longer than is typical and, thus, are said to be metastable, meaning relatively stable. Phosphorescence is the de-excitation of a metastable state. Glow-in-the-dark materials, such as luminous dials on some watches and clocks and on children’s toys and pajamas, are made of phosphorescent substances. Visible light excites the atoms or molecules to metastable states that decay slowly, releasing the stored excitation energy partially as visible light. In some ceramics, atomic excitation energy can be frozen in after the ceramic has cooled from its firing. It is very slowly released, but the ceramic can be induced to phosphoresce by heating—a process called “thermoluminescence.” Since the release is slow, thermoluminescence can be used to date antiquities. The less light emitted, the older the ceramic. (See Figure 6.)

Figure 6. Atoms frozen in an excited state when this Chinese ceramic figure was fired can be stimulated to de-excite and emit EM radiation by heating a sample of the ceramic—a process called thermoluminescence. Since the states slowly de-excite over centuries, the amount of thermoluminescence decreases with age, making it possible to use this effect to date and authenticate antiquities. This figure dates from the 11th century. (credit: Vassil, Wikimedia Commons)

Lasers

Lasers today are commonplace. Lasers are used to read bar codes at stores and in libraries, laser shows are staged for entertainment, laser printers produce high-quality images at relatively low cost, and lasers send prodigious numbers of telephone messages through optical fibers. Among other things, lasers are also employed in surveying, weapons guidance, tumor eradication, retinal welding, and for reading music CDs and computer CD-ROMs.

Why do lasers have so many varied applications? The answer is that lasers produce single-wavelength EM radiation that is also very coherent—that is, the emitted photons are in phase. Laser output can, thus, be more precisely manipulated than incoherent mixed-wavelength EM radiation from other sources. The reason laser output is so pure and coherent is based on how it is produced, which in turn depends on a metastable state in the lasing material. Suppose a material had the energy levels shown in Figure 7. When energy is put into a large collection of these atoms, electrons are raised to all possible levels. Most return to the ground state in less than about [latex]{10^{-8} \;\textbf{s}}[/latex], but those in the metastable state linger. This includes those electrons originally excited to the metastable state and those that fell into it from above. It is possible to get a majority of the atoms into the metastable state, a condition called a population inversion.

Figure 7. (a) Energy-level diagram for an atom showing the first few states, one of which is metastable. (b) Massive energy input excites atoms to a variety of states. (c) Most states decay quickly, leaving electrons only in the metastable and ground state. If a majority of electrons are in the metastable state, a population inversion has been achieved.

Once a population inversion is achieved, a very interesting thing can happen, as shown in Figure 8. An electron spontaneously falls from the metastable state, emitting a photon. This photon finds another atom in the metastable state and stimulates it to decay, emitting a second photon of the same wavelength and in phase with the first, and so on. Stimulated emission is the emission of electromagnetic radiation in the form of photons of a given frequency, triggered by photons of the same frequency. For example, an excited atom, with an electron in an energy orbit higher than normal, releases a photon of a specific frequency when the electron drops back to a lower energy orbit. If this photon then strikes another electron in the same high-energy orbit in another atom, another photon of the same frequency is released. The emitted photons and the triggering photons are always in phase, have the same polarization, and travel in the same direction. The probability of absorption of a photon is the same as the probability of stimulated emission, and so a majority of atoms must be in the metastable state to produce energy. Einstein (again Einstein, and back in 1917!) was one of the important contributors to the understanding of stimulated emission of radiation. Among other things, Einstein was the first to realize that stimulated emission and absorption are equally probable. The laser acts as a temporary energy storage device that subsequently produces a massive energy output of single-wavelength, in-phase photons.

Figure 8. One atom in the metastable state spontaneously decays to a lower level, producing a photon that goes on to stimulate another atom to de-excite. The second photon has exactly the same energy and wavelength as the first and is in phase with it. Both go on to stimulate the emission of other photons. A population inversion is necessary for there to be a net production rather than a net absorption of the photons.

The name laser is an acronym for light amplification by stimulated emission of radiation, the process just described. The process was proposed and developed following the advances in quantum physics. A joint Nobel Prize was awarded in 1964 to American Charles Townes (1915–), and Nikolay Basov (1922–2001) and Aleksandr Prokhorov (1916–2002), from the Soviet Union, for the development of lasers. The Nobel Prize in 1981 went to Arthur Schawlow (1921-1999) for pioneering laser applications. The original devices were called masers, because they produced microwaves. The first working laser was created in 1960 at Hughes Research labs (CA) by T. Maiman. It used a pulsed high-powered flash lamp and a ruby rod to produce red light. Today the name laser is used for all such devices developed to produce a variety of wavelengths, including microwave, infrared, visible, and ultraviolet radiation. Figure 9 shows how a laser can be constructed to enhance the stimulated emission of radiation. Energy input can be from a flash tube, electrical discharge, or other sources, in a process sometimes called optical pumping. A large percentage of the original pumping energy is dissipated in other forms, but a population inversion must be achieved. Mirrors can be used to enhance stimulated emission by multiple passes of the radiation back and forth through the lasing material. One of the mirrors is semitransparent to allow some of the light to pass through. The laser output from a laser is a mere 1% of the light passing back and forth in a laser.

Figure 9. Typical laser construction has a method of pumping energy into the lasing material to produce a population inversion. (a) Spontaneous emission begins with some photons escaping and others stimulating further emissions. (b) and (c) Mirrors are used to enhance the probability of stimulated emission by passing photons through the material several times.

Lasers are constructed from many types of lasing materials, including gases, liquids, solids, and semiconductors. But all lasers are based on the existence of a metastable state or a phosphorescent material. Some lasers produce continuous output; others are pulsed in bursts as brief as [latex]{10^{-14} \;\textbf{s}}[/latex]. Some laser outputs are fantastically powerful—some greater than [latex]{10^{12} \;\textbf{W}}[/latex] —but the more common, everyday lasers produce something on the order of [latex]{10^{-3} \;\textbf{W}}[/latex]. The helium-neon laser that produces a familiar red light is very common. Figure 10 shows the energy levels of helium and neon, a pair of noble gases that work well together. An electrical discharge is passed through a helium-neon gas mixture in which the number of atoms of helium is ten times that of neon. The first excited state of helium is metastable and, thus, stores energy. This energy is easily transferred by collision to neon atoms, because they have an excited state at nearly the same energy as that in helium. That state in neon is also metastable, and this is the one that produces the laser output. (The most likely transition is to the nearby state, producing 1.96 eV photons, which have a wavelength of 633 nm and appear red.) A population inversion can be produced in neon, because there are so many more helium atoms and these put energy into the neon. Helium-neon lasers often have continuous output, because the population inversion can be maintained even while lasing occurs. Probably the most common lasers in use today, including the common laser pointer, are semiconductor or diode lasers, made of silicon. Here, energy is pumped into the material by passing a current in the device to excite the electrons. Special coatings on the ends and fine cleavings of the semiconductor material allow light to bounce back and forth and a tiny fraction to emerge as laser light. Diode lasers can usually run continually and produce outputs in the milliwatt range.

Figure 10. Energy levels in helium and neon. In the common helium-neon laser, an electrical discharge pumps energy into the metastable states of both atoms. The gas mixture has about ten times more helium atoms than neon atoms. Excited helium atoms easily de-excite by transferring energy to neon in a collision. A population inversion in neon is achieved, allowing lasing by the neon to occur.

There are many medical applications of lasers. Lasers have the advantage that they can be focused to a small spot. They also have a well-defined wavelength. Many types of lasers are available today that provide wavelengths from the ultraviolet to the infrared. This is important, as one needs to be able to select a wavelength that will be preferentially absorbed by the material of interest. Objects appear a certain color because they absorb all other visible colors incident upon them. What wavelengths are absorbed depends upon the energy spacing between electron orbitals in that molecule. Unlike the hydrogen atom, biological molecules are complex and have a variety of absorption wavelengths or lines. But these can be determined and used in the selection of a laser with the appropriate wavelength. Water is transparent to the visible spectrum but will absorb light in the UV and IR regions. Blood (hemoglobin) strongly reflects red but absorbs most strongly in the UV.

Laser surgery uses a wavelength that is strongly absorbed by the tissue it is focused upon. One example of a medical application of lasers is shown in Figure 11. A detached retina can result in total loss of vision. Burns made by a laser focused to a small spot on the retina form scar tissue that can hold the retina in place, salvaging the patient’s vision. Other light sources cannot be focused as precisely as a laser due to refractive dispersion of different wavelengths. Similarly, laser surgery in the form of cutting or burning away tissue is made more accurate because laser output can be very precisely focused and is preferentially absorbed because of its single wavelength. Depending upon what part or layer of the retina needs repairing, the appropriate type of laser can be selected. For the repair of tears in the retina, a green argon laser is generally used. This light is absorbed well by tissues containing blood, so coagulation or “welding” of the tear can be done.

Figure 11. A detached retina is burned by a laser designed to focus on a small spot on the retina, the resulting scar tissue holding it in place. The lens of the eye is used to focus the light, as is the device bringing the laser output to the eye.

In dentistry, the use of lasers is rising. Lasers are most commonly used for surgery on the soft tissue of the mouth. They can be used to remove ulcers, stop bleeding, and reshape gum tissue. Their use in cutting into bones and teeth is not quite so common; here the erbium YAG (yttrium aluminum garnet) laser is used.

The massive combination of lasers shown in Figure 12 can be used to induce nuclear fusion, the energy source of the sun and hydrogen bombs. Since lasers can produce very high power in very brief pulses, they can be used to focus an enormous amount of energy on a small glass sphere containing fusion fuel. Not only does the incident energy increase the fuel temperature significantly so that fusion can occur, it also compresses the fuel to great density, enhancing the probability of fusion. The compression or implosion is caused by the momentum of the impinging laser photons.

Figure 12. This system of lasers at Lawrence Livermore Laboratory is used to ignite nuclear fusion. A tremendous burst of energy is focused on a small fuel pellet, which is imploded to the high density and temperature needed to make the fusion reaction proceed. (credit: Lawrence Livermore National Laboratory, Lawrence Livermore National Security, LLC, and the Department of Energy)

Music CDs are now so common that vinyl records are quaint antiquities. CDs (and DVDs) store information digitally and have a much larger information-storage capacity than vinyl records. An entire encyclopedia can be stored on a single CD. Figure 13 illustrates how the information is stored and read from the CD. Pits made in the CD by a laser can be tiny and very accurately spaced to record digital information. These are read by having an inexpensive solid-state infrared laser beam scatter from pits as the CD spins, revealing their digital pattern and the information encoded upon them.

Figure 13. A CD has digital information stored in the form of laser-created pits on its surface. These in turn can be read by detecting the laser light scattered from the pit. Large information capacity is possible because of the precision of the laser. Shorter-wavelength lasers enable greater storage capacity.

Holograms, such as those in Figure 14, are true three-dimensional images recorded on film by lasers. Holograms are used for amusement, decoration on novelty items and magazine covers, security on credit cards and driver’s licenses (a laser and other equipment is needed to reproduce them), and for serious three-dimensional information storage. You can see that a hologram is a true three-dimensional image, because objects change relative position in the image when viewed from different angles.

The name hologram means “entire picture” (from the Greek holo, as in holistic), because the image is three-dimensional. Holography is the process of producing holograms and, although they are recorded on photographic film, the process is quite different from normal photography. Holography uses light interference or wave optics, whereas normal photography uses geometric optics. Figure 15 shows one method of producing a hologram. Coherent light from a laser is split by a mirror, with part of the light illuminating the object. The remainder, called the reference beam, shines directly on a piece of film. Light scattered from the object interferes with the reference beam, producing constructive and destructive interference. As a result, the exposed film looks foggy, but close examination reveals a complicated interference pattern stored on it. Where the interference was constructive, the film (a negative actually) is darkened. Holography is sometimes called lensless photography, because it uses the wave characteristics of light as contrasted to normal photography, which uses geometric optics and so requires lenses.

Figure 15. Production of a hologram. Single-wavelength coherent light from a laser produces a well-defined interference pattern on a piece of film. The laser beam is split by a partially silvered mirror, with part of the light illuminating the object and the remainder shining directly on the film.

Light falling on a hologram can form a three-dimensional image. The process is complicated in detail, but the basics can be understood as shown in Figure 16, in which a laser of the same type that exposed the film is now used to illuminate it. The myriad tiny exposed regions of the film are dark and block the light, while less exposed regions allow light to pass. The film thus acts much like a collection of diffraction gratings with various spacings. Light passing through the hologram is diffracted in various directions, producing both real and virtual images of the object used to expose the film. The interference pattern is the same as that produced by the object. Moving your eye to various places in the interference pattern gives you different perspectives, just as looking directly at the object would. The image thus looks like the object and is three-dimensional like the object.

Figure 16. A transmission hologram is one that produces real and virtual images when a laser of the same type as that which exposed the hologram is passed through it. Diffraction from various parts of the film produces the same interference pattern as the object that was used to expose it.

The hologram illustrated in Figure 16 is a transmission hologram. Holograms that are viewed with reflected light, such as the white light holograms on credit cards, are reflection holograms and are more common. White light holograms often appear a little blurry with rainbow edges, because the diffraction patterns of various colors of light are at slightly different locations due to their different wavelengths. Further uses of holography include all types of 3-D information storage, such as of statues in museums and engineering studies of structures and 3-D images of human organs. Invented in the late 1940s by Dennis Gabor (1900–1970), who won the 1971 Nobel Prize in Physics for his work, holography became far more practical with the development of the laser. Since lasers produce coherent single-wavelength light, their interference patterns are more pronounced. The precision is so great that it is even possible to record numerous holograms on a single piece of film by just changing the angle of the film for each successive image. This is how the holograms that move as you walk by them are produced—a kind of lensless movie.

In a similar way, in the medical field, holograms have allowed complete 3-D holographic displays of objects from a stack of images. Storing these images for future use is relatively easy. With the use of an endoscope, high-resolution 3-D holographic images of internal organs and tissues can be made.

Section Summary

An important atomic process is fluorescence, defined to be any process in which an atom or molecule is excited by absorbing a photon of a given energy and de-excited by emitting a photon of a lower energy.

Some states live much longer than others and are termed metastable.

Phosphorescence is the de-excitation of a metastable state.

Lasers produce coherent single-wavelength EM radiation by stimulated emission, in which a metastable state is stimulated to decay.

Lasing requires a population inversion, in which a majority of the atoms or molecules are in their metastable state.

Conceptual Questions

1: How do the allowed orbits for electrons in atoms differ from the allowed orbits for planets around the sun? Explain how the correspondence principle applies here.

2: Atomic and molecular spectra are discrete. What does discrete mean, and how are discrete spectra related to the quantization of energy and electron orbits in atoms and molecules?

3: Hydrogen gas can only absorb EM radiation that has an energy corresponding to a transition in the atom, just as it can only emit these discrete energies. When a spectrum is taken of the solar corona, in which a broad range of EM wavelengths are passed through very hot hydrogen gas, the absorption spectrum shows all the features of the emission spectrum. But when such EM radiation passes through room-temperature hydrogen gas, only the Lyman series is absorbed. Explain the difference.

4: Lasers are used to burn and read CDs. Explain why a laser that emits blue light would be capable of burning and reading more information than one that emits infrared.

5: The coating on the inside of fluorescent light tubes absorbs ultraviolet light and subsequently emits visible light. An inventor claims that he is able to do the reverse process. Is the inventor’s claim possible?

6: What is the difference between fluorescence and phosphorescence?

7: How can you tell that a hologram is a true three-dimensional image and that those in 3-D movies are not?

Problem Exercises

1:Figure 10 shows the energy-level diagram for neon. (a) Verify that the energy of the photon emitted when neon goes from its metastable state to the one immediately below is equal to 1.96 eV. (b) Show that the wavelength of this radiation is 633 nm. (c) What wavelength is emitted when the neon makes a direct transition to its ground state?

2: A helium-neon laser is pumped by electric discharge. What wavelength electromagnetic radiation would be needed to pump it? See Figure 10 for energy-level information.

3: Ruby lasers have chromium atoms doped in an aluminum oxide crystal. The energy level diagram for chromium in a ruby is shown in Figure 17. What wavelength is emitted by a ruby laser?

Figure 17. Chromium atoms in an aluminum oxide crystal have these energy levels, one of which is metastable. This is the basis of a ruby laser. Visible light can pump the atom into an excited state above the metastable state to achieve a population inversion.

4: (a) What energy photons can pump chromium atoms in a ruby laser from the ground state to its second and third excited states? (b) What are the wavelengths of these photons? Verify that they are in the visible part of the spectrum.

5: Some of the most powerful lasers are based on the energy levels of neodymium in solids, such as glass, as shown in Figure 18. (a) What average wavelength light can pump the neodymium into the levels above its metastable state? (b) Verify that the 1.17 eV transition produces [latex]{1.06 \;\mu \text{m}}[/latex] radiation.

Figure 18. Neodymium atoms in glass have these energy levels, one of which is metastable. The group of levels above the metastable state is convenient for achieving a population inversion, since photons of many different energies can be absorbed by atoms in the ground state.

Glossary

metastable

a state whose lifetime is an order of magnitude longer than the most short-lived states

atomic excitation

a state in which an atom or ion acquires the necessary energy to promote one or more of its electrons to electronic states higher in energy than their ground state

atomic de-excitation

process by which an atom transfers from an excited electronic state back to the ground state electronic configuration; often occurs by emission of a photon

laser

acronym for light amplification by stimulated emission of radiation

phosphorescence

the de-excitation of a metastable state

population inversion

the condition in which the majority of atoms in a sample are in a metastable state

stimulated emission

emission by atom or molecule in which an excited state is stimulated to decay, most readily caused by a photon of the same energy that is necessary to excite the state

hologram

means entire picture (from the Greek word holo, as in holistic), because the image produced is three dimensional

holography

the process of producing holograms

fluorescence

any process in which an atom or molecule, excited by a photon of a given energy, de-excites by emission of a lower-energy photon